JP3643922B2 - Sweetener composition - Google Patents

Abstract

Powdery sweetener compositions having improved solubility, characterized by containing as the active ingredients powdery N- (3,3-dimethylbutyl)-L- alpha -aspartyl­-L-phenylalanine 1-methyl ester and powdery acesulfame-K at a ratio of acesulfame-K to the sum of these two components of 10 to 97% by weight.

Description

【００３５】
上表から、ＮＭＣ型結晶は、それが単独品である場合に比較して混合品（本発明の甘味料組成物）に配合されている形態の場合にその溶解性が顕著に改善されることが分かる。
【００３６】
なお、ＮＭおよびＡＣＥ−Ｋの甘味度は、前述のように、スクロースの約１０，０００倍および約２００倍である。この観点からは、混合品のサンプル１ｇの溶解所要時間と比較されるべきは、同一の甘味を得るに必要な量のＮＭの溶解所要時間ということになるが、このような比較によってもＡＣＥ−ＫにＮＭの溶解促進作用のあることは、例えば次の通りである。すなわち、ＡＣＥ−Ｋ粉体含量５０％の混合品１ｇの甘味は、ＮＭ単独品０．５１ｇの甘味に等しいが、前者の溶解所要時間４分に対し、後者のそれは約５５分であり、両者に顕著な差がある。
【００３７】
実験例２（ＮＭＡ型結晶とＡＣＥ−Ｋ粉体との混合品の溶解性）：
ＮＭＣ型結晶の代りにＮＭＡ型結晶を使用し、実験例１におけると同様にして、ＮＭとＡＣＥ−Ｋとの混合品の溶解所要時間を測定した。
【００３８】
混合品のサンプル量およびＮＭ単独品（ＮＭＡ型結晶）のサンプル量は、実験例１におけると同様とした。
【００３９】
各サンプルについての溶解所要時間（分）を下記第２表に示す。
【００４０】
【表２】

【００４１】
上表およびこれと第１表との比較から、ＮＭの溶解性は、Ａ型結晶よりもＣ型結晶の方がより顕著に改善せしめられることが分かる。
【００４２】
実験例３（ＮＭＣ型結晶単独品とＡＣＥ−Ｋ粉体の別投入）：
ＮＭとしては、実験例１におけると同じＮＭ結晶を採用し、またＡＣＥ−Ｋも実験例１におけると同じＡＣＥ−Ｋの粉体（平均粒径約２０μｍ）を採用して実験例１におけると同様にして溶解所要時間を測定した。
【００４３】
すなわち、両者からそれぞれ０．５ｇずつ分取し（合計１．０ｇ）、これらを事前に混合することなく、しかしながら同時に溶出試験機に投入した（別投入）。結果を下記第３表に示す。なお、参考までにＮＭＣ型結晶のみ０．５ｇの溶解所要時間（実験例１）も併記する。
【００４４】
【表３】

【００４５】
上表から、ＮＭとＡＣＥ−Ｋとを事前に混合することなく別投入したのではＡＣＥ−ＫによるＮＭの溶解性の改善はみられない。これは、ＡＣＥ−Ｋの溶解性が極めてよいことによるものと考えられることは、先に述べた通りである。
【００４６】
【発明の効果】
本発明に従い、ネオテーム（ＮＭ）にアセスルフェームＫ（ＡＣＥ−Ｋ）粉体を混合することにより、溶解性の悪いＮＭの溶解性を顕著に改善することができるとともに優れた甘味質の甘味料を容易に得ることができる。
【図面の簡単な説明】
【図１】Ａ型結晶の粉末Ｘ線回折図である。
【図２】Ｃ型結晶の粉末Ｘ線回折図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to powdered N- [N- (3,3-dimethylbutyl) -L-α-aspartyl] -L-phenylalanine 1-methyl ester (Neotem Neotama, hereinafter abbreviated as “NM”). The present invention relates to a powder sweetener composition having excellent solubility, comprising powdered acesulfame K (hereinafter abbreviated as “ACE-K”) as an active ingredient.
[0002]
[Prior art]
The sweetness intensity of the high-intensity synthetic sweetener NM has been reported to be about 10,000 times the weight ratio compared to sucrose (Japanese Patent Publication No. 8-503206). In addition, the details of the sweetness properties have not been reported, but according to the knowledge of the present applicant, the taste of taste (feeling sweetness as quickly as sucrose when included in the mouth) is extremely high. Weak and aftertaste (sweetness is felt slower than sucrose when in the mouth) is extremely strong. Also, astringency is strong. Therefore, the balance of sweetness characteristics is poor compared to sucrose, which is generally used as a standard for evaluation of sweetness characteristics.
[0003]
On the other hand, ACE-K is also a synthetic sweetener, and its sweetness intensity is about 200 times that of sucrose by weight, as in aspartame (hereinafter abbreviated as “APM”). The sweetness is further inferior, such as strong taste, bitterness, astringency, habit, and irritation, and the improvement of sweetness by the combined use with APM (US Pat. No. 4,158,068, Japanese Patent Publication No. 59 corresponding thereto) And various improvements have been proposed. Incidentally, the sweetness characteristics of APM are weaker and have a stronger aftertaste than sucrose, which is the standard for evaluating sweetness characteristics.
[0004]
Various proposals have been made for improving the sweetness of NM and ACE-K, and corresponding effects have been obtained. However, NM also has problems with solubility characteristics, ie, industrially produced NM powders (crystals) are poorly soluble (ie, forming lumps when trying to dissolve them in water). And the dissolution does not go smoothly, otherwise the dissolution rate is low). Poor solubility, such as the formation of lumps, lowers the production efficiency of foods and drinks containing NM for sweetening, such as soft drinks, which is a major disadvantage in their industrial production.
[0005]
[Problems to be solved by the invention]
Under the background of the prior art described in the previous section, an object of the present invention is to provide an excellent method for improving the solubility of NM.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to achieve the object described in the preceding paragraph, the present inventor does not form lumps when dissolved by mixing with ACE-K, and the dissolution rate is the dissolution of NM alone. The inventors have found an unexpected and unexpected fact that the rate is larger than the rate, that is, the solubility is improved as a whole, and the present invention has been completed based on such findings.
[0007]
That is, the present invention comprises N- [N- (3,3-dimethylbutyl) -L-α-aspartyl] -L-phenylalanine 1-methyl ester as powder and acesulfame K as powder as active ingredients. A powder sweetener composition, characterized in that the proportion of acesulfame K relative to the total amount of both is 10 to 97% by weight, and such a powder sweetener composition, The N- [N- (3,3-dimethylbutyl) -L-α-aspartyl] -L-phenylalanine 1-methyl ester is particularly in the form of C-type crystals and the proportion is 50 to 97% by weight About.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0009]
The powder NM, which is one of the active ingredients of the sweetener composition of the present invention, is not particularly limited in crystal form. For example, a known crystal (also referred to as A-type crystal) is a C-type crystal described later. Either may be used, but the latter is significantly superior to the former for the purposes of the present invention.
[0010]
In addition, the known crystal structure of NM disclosed in WO95 / 30689 is described therein as IR spectrum data. In addition, the present inventors have found that this crystal is a monohydrate as a result of single crystal structural analysis, and is at least 6.0 °, 24.8 °, 8. It was confirmed that specific peaks of diffraction X-rays were observed at diffraction angles of 2 ° and 16.5 ° (2θ, CuKα rays). The inventors have decided to refer to this crystal as an A-type crystal for convenience.
[0011]
As a result of further studies, the present inventors have found that the moisture content of the dried A-type crystal is usually 3 to 6% by weight (including water of crystallization). It has been found that when the water content is less than 3%, a new crystal of N- (3,3-dimethylbutyl) -APM with improved solubility from which water of crystallization is eliminated is obtained. I decided to call it a C-type crystal.
[0012]
This C-type crystal has a diffraction angle different from that of the A-type crystal when measured by powder X-ray diffractometry using CuKα rays, ie at least 7.1 °, 19.8 °, 17.3 ° and 17 °. A characteristic peak of diffracted X-rays is shown at a diffraction angle (2θ) of 0.7 °.
[0013]
See Reference Examples 1 to 3 below.
[0014]
The mixing ratio (use ratio) of NM and ACE-K in the sweetener composition of the present invention is 10 to 97% by weight as the ratio of ACE-K to both. When the use ratio of ACE-K is 10% by weight or less or 97% by weight or more, the dissolution promoting effect by ACE-K decreases.
[0015]
Even in such a mixing ratio of NM and ACE-K, the dissolution promoting effect on NM by ACE-K varies depending on the crystal form of NM. When NM is a C-type crystal and the ratio of ACE-K to the total amount of NM and ACE-K is 50 to 97% by weight, the solubility of NM is particularly improved.
[0016]
When both NM and ACE-K are pre-mixed at a predetermined ratio (the sweetener composition of the present invention) but separately but simultaneously into water (separate input), ACE-K has a dissolution rate. Although it is large and dissolves immediately, the dissolution rate of NM becomes rate-limiting and the dissolution rate is slower than that of the mixed product (Experimental Example 3 below).
[0017]
The sweetener composition of the present invention is a conventional high-intensity sweetener within the range that does not impair the improved solubility of NM according to the present invention for the purpose of improving usability or improving the quality of sweetness, depending on applications. As in the case of the composition, diluents and excipients such as sugar alcohols, oligosaccharides and dietary fiber, or other high-intensity synthetic sweeteners such as aspartame, alitame, saccharin, etc. be able to. Diluents and excipients in this case also include low sweetness sweeteners such as sucrose and glucose.
[0018]
According to the present invention, it is possible not only to further improve the solubility of NM, but also to produce an excellent sweetener composition with improved sweetness for both NM and ACE-K.
[0019]
【Example】
Hereinafter, the present invention will be further described with reference examples and experimental examples.
[0020]
Reference Example 1: Preparation of NM Gaseous hydrogen was introduced into a reactor equipped with a stirring blade that can surely make a very good transition to the liquid layer. . That is, 700 ml of ion-exchanged water, 4.21 ml of acetic acid, 20 g of 10% palladium carbon, 1,300 ml of methanol, 56 g of aspartame, and 25 ml of 3,3-dimethylbutyraldehyde.
[0021]
After filling the reactor with a stream of nitrogen gas, the reaction mixture was hydrogenated at room temperature at a flow rate of 200 ml / min. The progress of the reaction was monitored by sampling the reaction mixture and analyzing the product by high performance liquid chromatography (HPLC). After a 6 hour hydrogenation reaction, the reaction was stopped by filling the reactor with a stream of nitrogen gas and filtering the catalyst through a microporous filter (0.45 μm).
[0022]
As a result of analyzing the obtained filtrate (1,494 g), the yield was 81%. Subsequently, the filtrate was concentrated to 281 g, methanol was removed, and crystals were precipitated while stirring at 10 ° C. overnight. Finally, 87 g of NM white wet crystals (yield 77%) were obtained in high purity (> 99%, HPLC).
[0023]
Reference Example 2: Production of Type A Crystal Using a part of NM prepared in Reference Example 1, 100 g of an NM aqueous solution was prepared (dissolved at 60 ° C.) so that the concentration of NM was 3% by weight. Next, this was cooled from 60 ° C. to 30 ° C. with stirring over 5 minutes. When the liquid temperature reached 30 ° C., white crystals started to crystallize. The liquid temperature was kept at 30 ° C., and after aging overnight, the crystals were collected by filtration.
[0024]
(A) The wet crystal obtained above was measured for diffraction X-rays by a powder X-ray diffraction method using CuKα rays. The obtained powder X-ray diffraction pattern is shown in FIG.
[0025]
As is apparent from the figure, this wet crystal showed characteristic diffraction peaks at least at 6.0 °, 24.8 °, 8.2 ° and 16.5 °, and was an A-type crystal.
[0026]
(B) The wet crystal was placed in a vacuum dryer set at 50 ° C. and dried until the water content reached 5% by weight. The dried crystal thus obtained was measured by a powder X-ray diffraction method using CuKα rays, and as a result, it was also an A-type crystal.
[0027]
Furthermore, as a result of IR spectrum (KBr) measurement, it was in agreement with the value described in WO95 / 30689.
[0028]
Reference Example 3: Production of C-type crystal The above-mentioned dry A-type crystal having a water content of 5% by weight was dried with a vacuum dryer until the water content was continuously 0.8% by weight.
[0029]
The dried crystals were measured for diffraction X-rays by powder X-ray diffraction using CuKα rays. The obtained powder X-ray diffraction pattern is shown in FIG.
[0030]
As is apparent from the figure, the dried crystals showed characteristic diffraction peaks at least at 7.1 °, 19.8 °, 17.3 ° and 17.7 °. As mentioned earlier, this crystal is a C-type crystal.
[0031]
Experimental Example 1 (Solubility of a mixture of NMC type crystal and ACE-K powder):
Using a 1 L dissolution tester (Japanese pharmacy method, paddle method, 100 rpm), 900 ml (20 ° C.) of water was used, and a predetermined amount of sample was added thereto to measure the dissolution time (the end point was visually confirmed) .
[0032]
In detail, various ratios (ACE-K content (wt%)) shown in Table 1 below for NMC type crystals alone (average particle size of about 100 μm) and ACE-K powder (average particle size of about 20 μm) 1 g of each sample was taken from the mixed product, and each dissolution time was measured. For comparison, samples 1.00 g, 0.90 g, 0.80 g, 0.50 g, 0.10 g and 0.03 g were taken from the NM crystal, and the dissolution time was also measured.
[0033]
The required dissolution time (minutes) for each sample is also shown in Table 1 below.
[0034]
[Table 1]

[0035]
From the above table, the solubility of the NMC type crystal is remarkably improved in the case of the form blended in the mixed product (sweetener composition of the present invention) compared to the case where it is a single product. I understand.
[0036]
In addition, the sweetness degree of NM and ACE-K is about 10,000 times and about 200 times of sucrose as mentioned above. From this point of view, it should be compared with the dissolution time of 1 g of the sample of the mixture that the dissolution time of the amount of NM necessary to obtain the same sweetness. The fact that K has a dissolution promoting action of NM is as follows, for example. That is, the sweetness of 1 g of a mixture with an ACE-K powder content of 50% is equal to the sweetness of 0.51 g of NM alone, but the latter required about 4 minutes to dissolve, and the latter takes about 55 minutes. There is a noticeable difference.
[0037]
Experimental Example 2 (Solubility of a mixture of NMA type crystal and ACE-K powder):
The NMA type crystal was used instead of the NMC type crystal, and the time required for dissolution of the mixture of NM and ACE-K was measured in the same manner as in Experimental Example 1.
[0038]
The sample amount of the mixed product and the sample amount of the NM single product (NMA type crystal) were the same as those in Experimental Example 1.
[0039]
The dissolution time (minutes) for each sample is shown in Table 2 below.
[0040]
[Table 2]

[0041]
From the above table and a comparison between this and Table 1, it can be seen that the solubility of NM is significantly improved in the C-type crystal than in the A-type crystal.
[0042]
Experimental Example 3 (Separate input of NMC type crystal and ACE-K powder):
As NM, the same NM crystal as in Experimental Example 1 is adopted, and ACE-K also adopts the same ACE-K powder (average particle diameter of about 20 μm) as in Experimental Example 1, as in Experimental Example 1. Thus, the time required for dissolution was measured.
[0043]
That is, 0.5 g each was taken from both (total 1.0 g), and these were added to the dissolution tester simultaneously without mixing in advance (separate input). The results are shown in Table 3 below. For reference, the time required for dissolution of 0.5 g of only NMC type crystals (Experimental Example 1) is also shown.
[0044]
[Table 3]

[0045]
According to the above table, when NM and ACE-K are added separately without mixing in advance, the improvement of NM solubility by ACE-K is not observed. As described above, this is considered to be due to the extremely good solubility of ACE-K.
[0046]
【The invention's effect】
According to the present invention, by mixing acesulfame K (ACE-K) powder with neotame (NM), the solubility of NM with poor solubility can be remarkably improved and an excellent sweetness sweetener Can be easily obtained.
[Brief description of the drawings]
FIG. 1 is a powder X-ray diffraction pattern of an A-type crystal.
FIG. 2 is a powder X-ray diffraction pattern of a C-type crystal.

Claims (2)

As active ingredients, N- [N- (3,3-dimethylbutyl) -L-α-aspartyl] -L-phenylalanine 1-methyl ester in powder and acesulfame K in powder relative to the total amount of both. A powdered sweetener composition comprising acesulfame K in a proportion of 10 to 97% by weight. The powder N- [N- (3,3-dimethylbutyl) -L-α-aspartyl] -L-phenylalanine 1-methyl ester is a C-type crystal and the ratio is 50 to 97% by weight. The powder sweetener composition according to claim 1, wherein

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